Process for treating hydrocarbons



June 7, 1932- P. J. CARLJSLE ETAL PROCESS FOR TREATING HYDROCARBONSFiled Nov. 25, 1927 2 Sheets-Sheet 2 filPfwiji '35 a o 7 2 O 7 v o Q 7 a43 26 2a fi m/V6 Z5- 22 L 17 mm INZIENTORS BY W ATTORNEY Patented June7, 1932 U ITED STATES PATENT oFF cr.

h drocarbons,

rant aomvsou oanmsLn Am) cnnnnas nonnars Hams) NIAGARA m new Yonx,assrenons nr missus ASSIGNMENTS, cnnmrcan comranzor new Yon r, 1v. Y.,IA

raocnss ron 'rnna'rrne rrrnnooansous Application tiled November 25,

This invention These hydrocarbons may. e tained from any source, tion ofcrude petroleum, hydrocarbons, tion or extraction'of oil shale,gasoline, etc.- Our invention is also. applicable to the individualhydrocarbons as well as to mixtures. These untreated products areusually undesirable for use ecause of the presence of substances, suchas certain sulphur compounds and unstable hydrocarcracklng of heavybons, which have an unpleasant odor, whiclr resinifyon standing, etc.Thus in gasoline for motor usethese undesirables must here-- duced torender the product stable and saleable. In the succeeding specificationour 1n-,/

vention will be particularly described with reference to, what iscommonly known as gasoline, but we do not wish to be limited theretosince our invention is applicable to the treatment of hydrocarbons ingeneral.

The treatingof; crude gasoline usually results in the formation ofcertain solid and liquid by-products which may be polymers ofunsaturated compounds in the gasoline-or treating agent i ation, and maymay be compounds of certain constituents of the gasoline, or both. Ingeneral, such by-products are troublesome since they tend to r'oulthetreating apparatus and the treating agent. In many cases it isnecessary for economic reasons to recover the from its mixturevwith theof course, adds an. extra operproducts; this,

be attended with considerable difficulty and expense; This prohibits jthe use ofrelatively expensive treating baths or a process wherebytreating agents cven though theyproduce asuperior product.

' Thusfior example, suchdiiiicultiesform one of the principal reasonswly alkali metals have not bccnused commercially in treating .crudegasolines even though .itis known that the treated product is ofexcellent quality.

. Theobject of this invention is to provide the excessive fouling or theaccumulation of treatment lay-products in media for hydrocarbons isavoided. A further object is to provide a process whereby alkali metalsmay be used as treating agents undcrsuch conditions that relates tothetreatment of such s the distilla-V hydrogenation of coal, distilla- Iable.

the treating agent with a we do not wish CORPORATION i OF DELAWARE 1927.Serial N... 235,502.

without additional treating agent,and alsoremoving some suspendingliquid and contaminating by-products with it; these by products may bein suspension or solution or both. Thus, for example, the suspendingliquid may be a hydrocarbon of characteristics, boiling range, etc.,similar to the product removed as vapor but having a boiling point curvehigher than that of the vapor fraction (temperature as abscissae, volumeas ordinates) such a sus pending liquid would be formed from higherboiling constituents of the gasoline being treated. Other suspendingliquids of proper physical and chemical characteristics are suit- Thus,liquids, such as heavy oils, having much higher boiling rangesdrocarbons being treated would be suitable; so also, individualhydrocarbons of proper boiling point maybe used.

A great variety of treating agents may be used in our process; some ofthese arealuminum chloride, sodium,potassium, or alloys such as sodiumalloys with other alkali metals or .with alkaline earth metals, or withheavier metals as lead, mercury, and the like. We have'obtainedexcellent results with, for example, aluminum-chloride, sodium metal roTHE nonssnna a nassnacrmn than the hy- (solid and liquid), sodiumamalgam and sodium lead alloy.

In this specification. we speak of a suspension of the treatin to belimited to the physical condition of the medium that this may imply. \Vcdonot know whether-the success and particular cfiicacy of our method inproducing excellent products is due to the contact with undissolrcdagent in the liquid or to contact ble that with dissolved agent. It iseven possi some reaction product of component of the the agent and aliquid, or that certain subagent in liquid, but

stances produced by the treating process and included in the termpolymer or by-prodnot as used herein, may either in solution orsuspension, or both, contribute to the suc- 5 cess of the process. Inany event we intend e expressions treating agent ina liquid treatingagent in liquid hydrocarbon or suspension in a liquid, etc., to coverall these possible mg medium is meant th of which may be organiccompounds, some compounds of alkali metals, and some sulproduced fromhydrocarbons from different sources or from the same source at differenttimes.

Our preferred application of this general gsprinciple comprises passingthe hydrocarbons into contact with alkali metal in liquid hydrocarbonand effectbe atomized or hydrocarbon f vapors. mist, The treatment hemain portion thereof will remain in 5 the reaction vessel. Therefore, wedonot limit ourselves toany particular method of contacting thehydrocarbons ing medium becausethis can be done inmany i consisting ofsodium in liquid hydrocarbons.

condensinga part of the high boiling constitthe suspending liquid, re-

treating lots or other impurities reatment.

Figure I illustrates one form of apparatus physical conditions. By treate mixture of liquid tator may, under posed we will describe in th iisinvention which comprises suitable for applying the principles of thisinvention.

Figure II illustrates further adaptations of our inventionwith specialreference to the ydrocarbon are introduced through the pipe 1, which maycarry a condenser 2, through the opening treating mediuin 4, with levelat 5, and contained in a vessel or reactor 6. The vessel may be equippedwith an agitator 7. driven by the pulley 8 through the shaft 9. Theagicertain conditions, be omitted, the agitation being supplied by theva- H pors entering the treating medium. The vesse is equipped with aacket or a coil 10, W ich is used either for heating or for cool- "alve.12 and pipe 13.. I

A fraction, depending upon the treating temperature, of the hydrocarbonvapors enteringthe vessel 6 is condensed. This con- 'fraction leavesbattle separator 14 and pipe 15, and b a devicesuc as siphon 16, anapproximate y constant level 5 of the medium is maintained. This liquidis run through pipe 17 and disof inv various Ways.

The portion of the hydrocarbons leaving the reactor as vapor passesthrough the pipe 18, which may be equipped with a fractional condenser19 to'con ense out, if desired, an higher boiling constituents. Theliquid thus condensed can be passed into the treating vessel throughvalve 50 and pipe 51 or it can be removed through valve 52 and pipe 53and any desired way.

suitable recovery system, not shown here.

Exchanger 2 has been referred to as a condenser. Both 2 and the coil 10can be used either as treating temperature.

The liquid leaving the reactor by Way of separator 14 and pipe15consists of the heavier ends, that is, the higher boiling constituentsof the gasolines or hydrocarbons treated. This'liquid efliuent carrieswith it Inasmuch as the alkali metals are relatively light it isadvisable to provide a separator,

' bafiles as at 14, which will 7 r I Y from the liquid efiluen Theliquid eflluent may be handled in a number of ways. For example, withreference to Figure II, it may be sent by Way of valve of valve 42 andpipe 43, or, by way 37, to aproper point for evapora- 36 and pipe tion.cracking, etc. Or, the effluent in pipe 17 can be passed through valve44 and into a separating device 25 and subjected to or other method of130 fuging, filtering,

separation,

flowing into a container28 which acts as a feed reservoir for pumpTreatment by-products are shown as leaving the separating device at 26.The clarified liquid leaves by way of pipe 27,

30, the latter driven bymotor31. The pump receives the liquid throughpipe 29 and can deliver it through i pip liquid canbe caused to vessel,thus making tmuous operation .32 to any point desired. Thus, the flowthrough valves 33, 38, and -10, and pipe 39, into the treating itpossible with conand proper temperature control: to remove from thetreating as treated gasoline practically allot the gasoa jected todistillation,

polymerresidue 1 and the suspension 25 i those skilled in The metalmight cept that lost b line fed ex operation and as polymer.

disposed of as. desired. It is to be noted that the efiiuent has alsobeen subjectedto the treating action.

The alkali metalcan be fed to the reactor inany convenientmanner. It maybe prepared as-a suspension in liquid hydrocarbon added to. thereactorby way of hopperll or the metalmay he adde in solidfo-rm such asbricks andagitation" in the reactor will serve to subdivide it on beapplied by handling. such materials.

melting. Other methods may be added as a liquid or asa finely dividedmetal in suspension. method of making and applying colloidalsodiumconsists in passing a condensed electric sparkbetwen two sodiumelectrodes a suitable distance from each other placed at liquid suchasether, xylene, etc.:

under a Such a colloidal suspension isthen introduced directly into thetreating vessel. It is also possible. toy make the colloidal suspensiondirectly in the treating vessel itself.

The percentage of the hydrocarbons fed to 1 the treating apparatus whichleaves the reactor asliquid is regulated, in general, ac-

hydrocarbons so line as liquid and finished product. y 6 hydrocarbonsare removed almostentirely a same time a higher temperatureof'treatjment? p can be maintained,

stantially all 56 cording to the amount oi polymer formed.

removedto carry away Enoughsuchliquid must be condensed and the polymerat a satisfactory rate.

In some cases substantiallyall of the maybe removed as liquid.

There would be little point in doing thisif gasoline vapors are beinggasoline is introduced into as liquid it is entirely feasible toremovesub boiling constituent-s which might compose say up to 15Vpercentof the material) ofthe gasodistil it for recovery of the being treated,for example, lubricating oil stock, the hydrocarbons canbe as liquid andat the if desired. The efliu'ent liquid may be distilled or treatedbysuch methods as centrifuging, agitating with ab- Further, the e uent maybe sub: and the distillate and to a spare unit if d V metal collect-sOne . Thus, referring treating vessel.

treated, but if the the treating vessel (except perhaps the very lowestboiling liquid,

If higher. boiling liquid mcnt of hydrocarbon --va pors'; the

peratures even though at higher temperatures the treating medium foulsmore quickly per unit of hydrocarbons treated and the polymer has moreobjectionable physical properties than at lowertemperatures.

Operations utilizing higher temperatures may be carried outin at leastthree ways. Thusat intervals operation may be switched the first hasbecome excessively fouled. Then, because thealkali metals (exceptlithium) settle more rapidly than the polymer, a large part of thealkali in the lower end of the conical bottom of the treating vesselasat and day be drawn oil by valve '21 andpipe '22.

r bulk of the polymer which is suspendedin the medium settles down justabove the alkali metal most of thepolymer canbe removed,

along with a portion of the liquid medium, throughthe pipe 23 andvalve24;, after which the treating vesselis ready for further use. Accordingto the second method the polymer may be removed from the treating mediumby effecting a flow, circuit, of higher boiling hydrocarbon. to FigureII, higher boiling liquid in supply tauk 35 may be, caused to flowthrough valve fll'and pipe 47 into the treating vessel at a given rateand be removed through pipe 15, with the polymer,

the polymer separated from the liquid by filtering, centrifuging orother 25 and the liquid returned by pump through pipe 32 and valves 33and 34 to the supply tank 35 and'then to the It is obvious that thehigher boiling liquid neednot necessarily be returned to the circuit,butyinstead, since it settling, means as at has been treated once 1t maybe utilized, per

se, for finished products. In such cases fresh crude higher boilingfractions are introduced vessel. Some of the higher depending upon itsvapor ressure, leaves the trcatingvessel with the treated hydrocarbonvapors and, if necessary,1may be recovered by subjecting the treatedhydrocarbon vapors to-a partial coninto the treating ossihle to operatcnhaler pressure. I

Our invention,1s'not lin1ited to the treatapparatus may be utilizedfor-"liquid treatment. "For instead of removing the metal, since the soto speak, in a separate nsationgprocessii.-Asia third method it isinstance, liquid hydrocarbons can be introduced through pipe 1. In thiscase the coil can-be used as a heater. The same treating temperature canbe used which would be employed if the same hydrocarbons fwereintroducedas Vapors in which case the greater part of the treated hydrocarbonsleave the drocarbons of 14 and reactor as vapor through 18. Or, ifdesired, a lowertreating temperature can be used, such thatsubstantially all of the treated byleave the reactor as liquid by way15; the liquid passing, for example, directly to a still from which afinal product of good qualitygis obtained.

3.5 grams of sodium in 350 cc.

fluent or heavy ends froma previous run,

Ea'ampZe.This example serves as a spe cific illustration of thisinvention. The hydrocarbon mixture treated was crude, cracked gasolinemade by cracking certain fractions of Pennsylvaniacrude petroleum. 87.15liters of this liquid crude cracked gasoline was passed as vapor into adium consisting initially of approximately at an average rate of about1.0 liter per hour.

7 The temperature of the treating medium was maintained at 150.155 Atintervals of about, 8 hours of running time additional sodium was addedto the treating medium. These additions consisted of 2 to 3 grams of themetal in the form of sodium shot. tinned the treating lent condition anda medium was in excelhigh quality of product I was still being obtained.

69.865 liters of refined gasoline and 15.07 liters of liquid-polymerfractionwere recovered. The; loss of hydrocarbons was 2.215 liters orabout 2.54 .percent by volume of the'feed. The 15.07 liters of liquidof: fluent amountedto about 17.3 percent of the feed. Approximately90percent by volume ofthis liquid to that of the was gasoline of end pointequal crude gasoline before treatment as shown in the distillation dataof Table I.

The total weight of sodium introduced into thetreating medium for theWhole run was 39.5 grams. At the end of the run 12.25 grams of sodium"remained in the treating vessel. The sodium consumer, therefore, was27.25 grams which corresponds to about 0.313 grams per liter or about0.11 pound per barrel (42 gallons) of crude gasoline fed.

Table I shows the distillation data for the the reaction medium is.poscertain cracked gaso treating meof liquid ef- WVhen the run wasdiscon- 1. e., sodium, potassium,

' or with other vapors leaving'the treating crude cracked gasolinebefore treatment, the

Crude cracked gasol Refined gasoline Liquid emuent 1 I Percent Temp. iPercent (115- Temp. distilled F. tilled F.

Residue 1% Residue Loss L Residue 10% Table 11' Crude gasoline g gaso-MR "Unsaturated" hydrocarbons 12. 33% 10. 5 Aromatic hydrocarbons 24. 3%24. 9% Naphthenio hydrocarbons 31.1% 32.8% Paraffin hydroearbons 32. 27%31. 8% Sulphur (lamp method) 0' 0195% 0.007% Doctor test 1 PositiveNegative. Copper strip corrosion test Positive. Negative. Odor f"Sulphurnus Sweet. Color About 18. Water-white.

The excellent color stability of the refined gasoline fraction is shownby the factthat subjected to sunl'ghtifor 7 days the color changed from30 to 25; other samples placed in a window for 7 days changed incolorfrom -30 to 28; other samples exposed to darknessfor 7 dayssuffered no appreciable change in colon.

In order to avoid ambiguity and a multiplicity of claims the followingdefinitions of' the terms used in the claims are here given: The termalkali metal etc., singly or in various combinations or mixtures witheach other metals such ascalcium, mag nesium, mercury, lead. tin. etc.,in any applicable physical state. The term by-products covers all of thesubstances that are formed in the treating medium and that are notremoved with the treated hydrocarbon vessel. The

term hydrocarbons stands for mineral oils,

rials that may gasolines, and any other be improved hydrocarbon mateasherein described. liquid is meant bons substantially as 3 medium comrising sodium suspended inliqproducts ,bonsintoa treatin metal suspendedunreacted alkali q 2. Process comprising passing hydrocar- 1 edhydrocarbon 1; Process comprising contacting hydrocarbons liquid atthereaction temperature with a treating medium comprisin an alkali liquidhydrocarbon,

metal suspended in washing contaminating by-products from said alkalimetal by agitation with the suspending medium, and removing treatedhydrocarbonifromthe treating medium as liquid effluent, after uidhydrocar on, washing contaminating byfrom said sodium by agitation withthe suspending medium, and removin treatr'rom the treating me ium asliquid efliuent. i q 4:. Process comprising passing hydrocarmediumcomprising alkali in liquid hydrocarbon having a boiling point curvehigher than that metal from an efiiuent portion,

of the hydrocarbon introduced, removing treated hydrocarbon from thetreating medium as vapor, washing contaminating byproducts from saidalkali metal by agitation with said higher boiling hydrocarbon flowinthroughthetreating vessel, separating su stantia ly all washed unreactedalkali and discharging suspended contaminating byaproducts byagitationwith 0 carbon, separating from the treating vesselsuspende in saidefliuent before fouling quantities accumulate.

a 5., Process comprislng passing hydrocarbons substantially as vaporsinto a treating medium comprising suspended sodium in liqui'dhydrocarbon having a boiling point curve higher than that of thehydrocarbon introduced and removin treated hydrocarbon from the treatingme ium as vapor, washing contaminating by-products from saidsodium saidhigher boiling hydrosubstantially all unreacted sodium \from a portionofsai hydrocarbon, flowing said portion from the treating vessel vat such;a rate that suspended contaminating by-products are discharged from thetreating vessel before fouling quantities accumulate.

y such treatment comprising alkali metal suspende dium partially asvapor,

*6. Process comprisin passing hydrocarbons at least partiallydiquidunder the reaction conditions into a treatin medium d in liquidhydrocarbon, washing said alkali metal by agitationwith said liquid andremoving treated hydrocarbon from the treating meand partially as liquideflluent, separating substantially all unreacted alkali metal from saideffluent before discharging it from the treating vessel.

Process comprising passing hydrocarbons substantially as vapors into atreating medium comprising sodium suspended in liquid hydrocarbon,washing said sodium by agitation with said liquid hydrocarbon andremoving treated hydrocarbon from the treating medium partially asvapor, and partially as liquid effluent, while separating substantiallyall unreacted sodium from said effluent before discharging it from thetreating vessel.

8. Process comprising contacting hydrocarbons at least partially liquidunder the reaction conditions with a treating medium comprisingalkali-metal suspended in liquid hydrocarbon having a boiling pointcurve higher than that of the hydrocarbon introduced and removingtreated hydrocarbon from the treating medium partially as vapor andpartially as liquid efiluent, separating substantially all unreactedalkali metal from said efiiuent before discharging it from the treatingvessel, and removing treatment byproducts from the medium with saidliquid efliuent. Y i

9. Process comprising contacting hydrocarbons at least partially liquidunder the reactionconditions-with a treating medium comprising sodiumsuspended in liquid hydrocarbon having a boiling point curve higher thanthat of the hydrocarbon introduced and removing treated hydrocarbon fromthe treating medium partially as vapor and partially as liquid efiluent,separating substantially all unreactedsodium from said eflluent beforedischarging it from the treating vessel, and removing treatmentby-products from the medium with said liquid efiluent.

10. Process comprising passing hydrocarbons substantially as vaporsintov a treating medium comprising a treating agent suspended in liquidhydrocarbons having a boiling point curve hi her than that of thehydrocarbon introduced; removing treatment byproducts from themediumwith a liquid effluent continuously-flowing from said treating medium atsuch rate that fouling quantitles of said by-productsdo not accumulatewithin the treating vessel, while continuously separating substantiallyall unreacted treating agent from said effluent before discharging fromthe treating vessel, said treating agent being continuously retainedsuspended in the said hydrocarbons and withinthe treating vessel.

I introduced; washing treatment by-products from said alkali metal byagitation with said suspending liquid; removing treatment byproductsfrom the medium with a liquid effluent continuously flowing from saidtreating medium at such rate that fouling quantities of said by-productsdo not accumulate within the treating vessel, while separatingsubstantially allunreacted alkali metal from said effluent beforedischarging from the treating vessel.

12. Process comprising bons substantially as vapors into a treatingmedium comprising sodium suspended in liquid hydrocarbons having aboiling point" curve higher than that of the hydrocarbon introduced;washing treatment by-products from said sodium by agitation With saidsuspending liquid removing treatment by-products from the medium with aliquid eii'luent continuously flowing from said treating medium at suchrate that fouling quantities of said by-products do not accumulatewithin the treating vessel, while separating substantially all unreactedsodium from said effluent before discharging from the treating vessel.

13. Process comprising contacting hydrocarbons at least partially liquidunder the reaction conditions with a treating medium comprising alkalimetal supended in liquid hydrocarbon and removing treated hydrocarbonfrom the treating medium partially as vapor and partially as liquideffluent, separating substantially all unreacted alkali metal from saidefiluent before discharging it from the treating vessel, and removingtreatment byproducts from the medium With said liquid effluent.

14. Process comprising passing hydrocarbons substantially as vapors intoa treating medium comprising alkali metal suspended in liquidhydrocarbon and removing treated hydrocarbon from the treating mediumpartially as vapor and partially as liquid effluent, separatingsubstantially all unreacted alkali metal from said efiiuent beforedischarging it from the treating vessel, and removing treatmentby-products from. the medium with said liquid efiluent. 1

15. Process comprising contacting hydrocarbons, at least partiallyliquid under the reaction conditions, with a treating medium comprisinga treating agent suspended in liquid hydrocarbon, removing'treatedhydrocarbon from the treating medium partially as vapor and partially asliquid effluent, continuously discharging treatment by-productssuspended in said effluent from the treating vessel, whilesimultaneously separating subpassing hydrocan' stantially all unreactedtreating agent from said eflluent before its discharge from the treatingvessel and continuouslyretaining saidagent suspended insaid liquidhydrocarbon in said vessel.-

16. Process comprising-passing hydrocarbons substantially as vapors intoa treating medium comprising alkali metal suspended in liquidhydrocarbon and removing the treated hydrocarbon from the treatingmedium partially as vapor and partially as liquid eflluent, separatingsubstantially all unreacted-alkali metal from saidefiluent beforedischarging it from the treating vessel, removing treatment by-productsfrom the medium with said liquid effluent and separating the by-productsfrom said liquid.

17. Process comprising contacting hydrocarbons atleast partially liquidunder the reaction conditions with a treating medium comprisingatreating agent suspended in liquid hydrocarbon and removing treatedhydrocarbon from the treating. medium partially as vapor and partialyfasliquid efiuent, separating substantially all unreacted treating agentfrom said efliuent before discharging it from the treating vessel,removing treatment by-products from the medium with said liquidetiiuent, separating'the byproducts from said liquid and recycling saidliquid through the treating vessel.

18. Process comprising passing hydrocarbons substantiall as vapors intoa treatin medium comprising alkali metal suspended in liquid hydrocarbonandremoving treated hydrocarbon from'the treating medium partially asvapor and partially as liquid eflluent, separating substantially allunreacted alkali metal from said effluent before discharging it from thetreating vessel, removing treatment by-products from the medium withsaid liquid effluent, separating the by-products from said liquid andrecycling said liquid through the treating vessel.

19. Process comprising contacting hydrocarbons, at least partiallyliquid under the reaction conditions, with a treating medium comprisinga treating agent suspendedin liquid hydrocarbon having a boiling pointcurve higher than that of the hydrocarbon treated, washing said treatingagent by agitation with said suspending hydrocarbon, continuouslyremoving treated hydrocarbon from the treatingmediums partially as vaporand partially as liquid cfiluent, continuously discharging treatmentby-products suspended in said liquidetfiuent, while simultaneouslyseparating substantially all unreacted treating agent from theefiiuentbefore its discharge from the treating vessel, and continuouslyretaining said agent suspended in said liquid hydrocarbon withinsaidvessel, and thereafter separating by-products from the liquid effluent.1 7

20. Process comprisingcontacting hydrocarbons at leastdpartially liquidunder the naction conditions with a treating. medium comprising atreating agent SIISPOndGd in U liquid hyt'lrocarbon' having bon from thetreatingmedium, partially as {I vapor and partially as liquid efiluent,sepavessel, separatingthe rate that fouling rating substantially allunreacted treating agent troin said efiiuent before discharging it fromthe treating vessel, removing treat meut by-products from the mediumwith said liquid eflluent, which is flowed out at such a quantitiesdo'not accumulate within the treating medium and treating by-productsfrom said liquid and recycling said liquid through the i with a treatingmedium comprising sodium treating vessel.

21. Process comprising contacting hydrocarbons liquid at the reactiontemperature suspended in liquid hydrocarbon, washing contaminatingby-products from said sodium by agitation with said liquid hydrocaringvesseLand bon, and removing treated hydrocarbon from the treating mediumas liquid efliuent,

separating substantially all unreacted sodium before discharging saidefiluent from the treating vessel. i

' 22. Process comprising contacting hydrocarbons at least partiallyliquid under the reaction conditions with a treating medium comprisingsodium suspended in liquid bydrocarbon and removing treated hydrocarbonrfrom thetreating medium partially as as liquid effluent; sepaallunreacted sodium before discharging said eflluent from the treatremovingtreatment by-prod ucts from the medium with said liquid efiiuent. i

28. Process comprising contacting hydrocarbons at least partially liquidunder the eiiiuent, separating said by-products from reaction conditionswith a treating, medium comprising sodium suspended in liquid hy-' itdrocarbon and removing treated hydrocar bon trom the treating medium)artially as vapor and partially as liquid e uent; sepad ratingsubstantiallyall unreacted sodium be- 5 fore discharging said efiluentfrom the treat-- ing vessel, removing treatment by-products from thetreating medium with said liquid said liquid and recycling said liquidthrough the treating vessel.

24. Process comprising passing hydrocarbons substantially as vapors ntoatreating medium comprising a treating agent suspended in liquidhydrocarbons having a boiling point curve higher than that of thehydrocarbon introduced, continuously condensing a sufiicient portion ofintroduced hydrocarbon to suspend and remove treatment byproducts withthe overflow of said liquid from the treating vessel, and simultaneouslyand continuously separating substantially all unreacted treating agentfrom said overflow unreacted alkali metal from said overflow.

26. Process comprising passing hydrocarbons substantially as vapors intoa treating medium comprising sodium suspended in liquidhydrocarbon"having a boiling point curve higher than that of thehydrocarbon introduced, condensing a suiiicient portion of saidhydrocarbon vapors insaid medium to suspend and remove treatmentby-products with overflow of said liquid hydrocarbon from the treatingvessel while separating Within the treating vessel substantially allunreacted sodium from said overflow.

27. Process comprising passing hydrocarbons substantially as vapors intoa treating medium comprising alkali metal suspended inliquid hydrocarbonunder such conditions that a part of the introduced hydrocarbpns leavesthe treating medium as vapor and a sufficient part is condensed in themedium to wash contaminating by-products from said alkali metal and byits outflow to remove byproducts at such rate that fouling quantities donot accumulate within said medium.

Process for treating hydrocarbon vapors which comprises subjecting them'to fractional condensation in a treating medium, comprising alkali metalsuspended in liquid previously produced by such condensation and washingcontaminating by-products from i substantially all unreacted alkalimetallicfore discharging said efiiuent. t

30. Process for treating hydrocarbonvapors which comprises subjectingthem to fractional condensation and treating them in a treating mediumcompr sing alkali metal vaporswith a medium suspended in liquidpreviously produced by such condensation, said medium being maintainedat such temperature as to maintainas tl -hq1nd substantially all thecondensate pre viously produced, and flowing out a portion of saidcondensate carrymg treatment by- 7 products after separating therefromsubstantiallyall unreacted alkali metal.

Process for treating hydrocarbon vapors which comprises fractionall'ycondensing a portion of said hydrocarbons and passing thevaporsremaining into a medium formed by suspendin r alkali metal inahydrocarbon liquid obtained by such fractionation, removingcontaminating b'y-products from said alkali metal by agitation with saidliquid and discharging by-products suspended in a portion thereof afterseparating substantially all unreacted alkali metal therefrom. I

32: Process for treating hydrocarbon vapors which comprises passing themin contact with alkali metal suspended'in liquid hydrocarbon maintainedat such a tempera ture that a sufiicient fraction of said vapors iscondensed in said liquid hydrocarbon, to

from the treatin Niagara and uent and recoverin Signed at Niagara Falls,State of New day of November, A. D. 1927. 1

PAUL JOH CHARL discharge contaminating by-prod'ucts suspended therein atsuch a rate that fouling amounts do not accumulate within saidcontacting liquid. ,s v

33. In a process for treating hydrocarbon vapors with alkali metal, thestep which comprises removing solid treatment by-products from saidalkali metal by means of liquid hy- 'drocarbon, while separating andretaining unreacted metal within the treating vessel and dischargingsaid by-products suspended in an efliuent portion of said liquid.

34. In a process for treating hydrocarbon I vapors with alkali metal,the step which comprises removing solid treatment by-products from saidalkali metal by means of liquid hydrocarbon obtained by condensing aportion of said hydrocarbon vapors, while separating and retainingunreac-ted metal within the treating Vessel'and discharging saidby-products suspended in an efiluent portion of said liquid.

35, In a process for treating hydrocarbon consisting of alkali metalsuspended in liquid hydrocarbon, the step which comprises fractionallycondensing a suflicient portion of saidvapors to furg zone afterseparating substantially allunreacted' sodium from this'ef g treatedhydrocarbons. in the county of York, this 19th NSON CARLISLE. as ROBERTSHA'RRIS.

